Diaphragm electrolyzer for production of chlorine,hydrogen and alkalies



cs. M. KAMARJAN 3,461,057 DIAPHRAGM ELECTROLYZER FOR PRODUCTION OFCHLORINB HYDROGEN AND ALKALIES Aug. 12, 1969 4 Sheets-Sheet 1 Filed Aug.20. 1964 FIEJ F'IGZ 2, 1969 c; M. KAMARJAN 3,461,057

DIAPHRAGM ELECTROLYZER FOR PRODUCTION OF CHLORINE, HYDROGEN AND ALKALIESFiled Aug 20. 1964 4 Sheets-$heet z FIIZIO F'IETU 1 2, 1969 G. M.KAMARJAN 3,461,057

- DIAPHRAGM ELECTROLYZER FOR PRODUCTION OF CHLORINE, HYDROGEN ANDALKALIES Filed s- 0. 1964 4 Sheets-Sheet s 1969 c; M. KAMARJAN 3,461,057

DIAPHRAGM BLECTROLYZER FOR PRODUCTION OF CHLORINE, HYDROGEN AND ALKALIESFiled Aug. 20, 1964 4 Sheets-Sheet 4 "E1111 EDS IZIZHIIJ r :::t:::1

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United States Patent 3,461,057 DIAPHRAGM ELECTROLYZER FOR PRODUCTION OFCHLORLNE, HYDROGEN AND ALKALIES Georgy Mikirtychevich Kamarjan,Vorontsovskaja Str., 30-h, Apt. 18, Moscow, U.S.S.R. Filed Aug. 20,1964, Ser. No. 390,843 Int. Cl. C22d 1/02; 301k 3/10 US. Cl. 204-258Claims ABSTRACT OF THE DISCLOSURE A diaphragm electrolyzer having setsof identical elementary electrolytic cells consisting of anode andcathode sets and a diaphragm. The cells are housed in a commonstationary casing divided with partitions into a plurality of similarsections.

The present invention relates to apparatus for production of chlorine,hydrogen and alkalies by means of electrolysis of chloride solutionsemploying a diaphragm method.

Hitherto the eificiency of modern diaphragm electrolyzers for productionof chlorine, hydrogen and alkalies, was increased by enlarging the unitsby increasing the number of electrolytic cells, as well as by increasingthe electrolysis current density.

As a rule, in the electrolyzers of high output, such as Huckers,Billiters, Daws, etc., the floor space occupied by the electrolyzers isincreased proportionally to the output of the electrolyzers; the weightof all the operating elements and components, such as a cathode, set ofanode plates, 21 cover, busbars, is increased in accordance with thedimensions of these electrolyzers.

The considerable size of the electrolyzers, the great weight of theiroperating elements and components make maintenance and installation ofthe electrolyzers difiicult since it is necessary to employ powerfulhoisting-handling equipment, to enlarge the floor area of repair shops,to widen passages in a row and between the rows of electrolyzers.

The designs of anode power supply systems in the known electrolyzersconsist in the following:

In case of lower power supply the set of anode plates is lead-filled inthe bottom of said electrolyzers, this design making difiicult theinstallation of the cathode and an adequate installation of the anode inthe electrolytic cell.

In case of upper power supply the installation of the anodes in thecover of a high output electrolyzer makes the whole construction toocumbersome.

Moreover, the anodes secured in the cover are at a low location whichhinders the removal of chlorine from the electrolysis zone.

In the electrolyzers known at present the power supply to the cathodescreen is usually eliected only along the upper and lower perimeters ofthe contact area between the cathode and the casing, thus resulting inincreased losses of voltage in the cathode.

All these drawbacks reduce the efliciency of modern powerful diaphragmelectrolyzers.

An object of the present invention is to provide a powerful diaphragmelectrolyzer which is characterized by maximum output per unit of thefioor space, is easily dismantled and reassembled when repairing it andreplacing diaphragms and sets of anode plates, has a long service lifeand a reliable protection of the current-carrying parts and the casingfrom corrosion, minimum losses of current in the busbars, contacts andelectrodes, and insures free evolution of gas from the electrolysiszone, as well as stable operation.

3,461,057 Patented Aug. 12, 1969 "ice The above objectives are achievedby a diaphragm electrolyzer for production of chlorine, hydrogen andalkalies comprising a set of identical elementary electrolytic cellsconsisting of anode and cathode sets and a diaphragm and being housed ina common stationary casing, said casing being divided with partitionsinto a plurality of similar sections to house said elementary identicalelectrolytic cells, the anode set of the cells being made as a set ofanode plates secured on a common base, the anode set also beinginstalled on the insulated bottom of the electrolyzer casing. Thecurrent to the anode sets is supplied through a busbar which is commonfor all the anodes, and is located at the top, said busbar beingconnected through a slot in the lining of the elementary electrolyticcell wall to the lower parts of the anodes in the plate. The current canbe also supplied to the anode sets from the top through a busbar whichis common for all the anodes, and is connected to metal clamps holdingthe contact parts of the anodes and passing current to them.

The anode sets of the elementary electrolytic cells can be manufacturedas vertical units composed of vertical rows of horizontally locatedgraphitized plates installed one on another, with side location of thecurrent leads to the vertical rows of the anodes, while every twovertical rows of anodes have common current leads at the both sides ofwhich said rows are positioned, said current leads being housed in achlorine-resistant supporting frame. Each vertical row can have its owncurrent leads located inside the chlorine-resistant frame.

The cathodes of the elementary electrolytic cells are manufactured astwo rows of box-shaped cathode elements united by a central housing,said cathode elements being symmetrically located relative to thecentral housing.

The cathodes of the elementary electrolytic cells can be alsomanufactured as two rows of box-shaped cathode elements united by acentral housing, said cathode elements being symmetrically locatedrelative to the central housing-screen, said cathode elements beingprovided with special slots for inserting and protecting the edges ofthe laminated diaphragms, said slots being located at the edges of thecathode pockets in the upper and lower parts of the central housing. Theelementary electrolytic cells can be equipped with cathodes havingcathode cells formed by box-shaped cathode elements, the width of saidelements corresponding to the thickness of the anodes irrespective ofwear.

In compliance with the invention, the cathodes of elementaryelectrolytic cells may be also equipped with current leads running fromthe top through a slot in the lining of the elementary electrolyticcell.

Other objects and advantages of the invention will be made apparent fromthe below description and the accompanying drawings in which:

FIG. 1 is a top partial sectional view of the electrolyzer with a loweranode power supply;

FIG. 2 is a side partial sectional view of the electrolyzer with a loweranode power supply;

FIG. 3 is a plan view of an elementary electrolytic cell with a sideanode power supply and with anodes located symmetrically relative to theframe carrying said anodes;

FIG. 4 illustrates the location of anodes with a side power supply inthe electrolyzer;

FIG. 5 is an elementary electrolytic cell with a side anode power supplyand one-sided location of the anodes relative to the frame carrying saidanodes;

FIG. 6 illustrates the location of anodes and cathodes in the insulatedcells;

FIG. 7 is a cathode with slots for inserting the edges of the laminateddiaphragm;

FIG. 8 is a plan view partially in section of the elec trolyzer with theanodes having one common lead of the feeding busbar common for saidanodes, said lead passing through the lining of walls;

FIG. 9 is a section taken along 9-9 and 9'9 in FIG. 8;

FIG. 10 is a plan partial sectional view illustrating the fastening ofanode plates to the current carrying busbar;

FIG. 11 is a side view, partly in section, illustrating the fastening ofcathode plates to the current carrying busbar;

FIG. 12 is a plan of the anode set; and

FIG. 13 is a side partial view of the cathode set.

The diaphragm electrolyzer in accordance with the invention comprises aset of identical, comparatively small elementary electrolytic cells 1rated at a definite load, said cells being located in a common casing 2of a unit, said casing being divided with partitions 3 into sectionswhich serve to house elementary electrolytic cells 1.

The output of such an electrolyzer depends upon the number and capacityof the elementary electrolytic cells.

The elementary electrolytic cells can be dismantled and removed from thecasing during repair or maintenance, while the casing itself is to befixedly installed.

Elementary electrolytic cells 1 housed in the common casing include sets4 and 5 of anodes and cathodes, respectively, with electric busbars,said cells operating quite independently from the point of view ofelectrolysis products and current.

Each elementary electrolytic cell can be fitted with an individual cover6 having brine inlets 7 and holes 8 for discharge of chlorine, as Wellas pipe unions 9 and 10 to discharge hydrogen and alkali, respectively.

The elementary electrolytic cells can be housed in one casing and not beinsulated as to the electrolyte (FIG. 3). In this case each elementarycell is to be series-connected to the respective elementary cells of theneighboring (in series) electrolyzers, the number of the busbarsconnecting two neighboring (in series) electrolyzers being equal to thenumber of elementary electrolytic cells in the electrolyzer, and eachbusbar being rated at the load of the elementary electrolytic cell.

Elementary electrolytic cells can be housed in one casing and beinsulated as to the electrolyte (FIGS. 5 and 6). In this case eachelementary electrolytic cell is seriesconnected to the other cellswithin one electrolyzer, the electrolyzing units of one series beingcoupled with each other irrespective of their output, with one electricjumper rated at the load of one elementary electrolytic cell.

The anode set of each elementary electrolytic cell is a plurality ofspecially located graphitized plate anodes 11 with a power supply systemand a contact protectiv device.

The anodes are installed in parallel rows in the electrolytic cellsformed by box-shaped cathode elements 12. The anodes can be fitted withlower current leads (FIGS. 1 and 2) or side current leads (FIGS. 3 and4).

It is preferable to use a lower anode power supply through busbar 13,common for the set of anodes and being brought upwards through thelining of the elementary electrolytic cell walls (FIG. 1). In this casethe lower parts of the anodes of each row are coupled with anode busbars14 (FIG. 9), said busbars being formed as copper or steel clamps, boltedto the edges of the graphitized plates.

All the anode busbars are connected by bolts to anode busbar-collector15 which, in turn, is connected to the output anode busbar.

All the contact parts of the anodes together with the anode busbars andthe common anode busbar, located in concrete trough-shaped base 16 ofthe anode set of the elementary electrolytic cell, is filled up withbituminol layer 17, and then with cement 18 to protect them from theeffect of chlorine and the electrolyte. The part of the common anodebusbar is also protected by any of the know means from the effect ofchlorine and anolyte.

The anode set made as a concrete plate with the immersed contact partsof the anodes, located in parallel rows, and with protruding parts ofsaid anodes, is installed on the bottom of the electrolyzer casing sothat the common anode busbar enters respective slot 19 in the lining ofthe elementary electrolytic .cell wall and its contact end runs upwardbetween the wall and the cover of the elementary electrolytic cell. Toprotect the common anode busbar from the effect of chlorine andelectrolyte, the slot is filled with bituminol and cement.

The use of the anode sets with the lower power supply and the output ofthe common anode busbar at the top, significantly simplifiies theinstallation of electrolyzers and, in particular, the installation ofthe cathodes of the elementary electrolytic cells. The employment ofmetal clamps, serving as anode busbars, for installation of the anodeset does not require any use of expensive lead and permits adjustment ofthe position of the anodes during the assembly.

The electrolyzer output can be effectively increased without enlargingthe floor space occupied by the electrolyzer, by extending the electrodesurfaces in height. However, the use of electrodes extended in heightwith lower or upper power supply results in great losses of voltage,while the combination of the lower anode power supply with the upper onegreatly complicates the anode power supply system and createsdifficulties in the use of electrolyzers.

In compliance with the proposed invention, electrodes extended in heightcan be used in case the elementary electrolytic cell has a side currentlead into its electrodes. In this case the anode set of the elementaryelectrolytic cell (FIG. 4) comprises vertical units located in rows. Theunits are composed of graphitized plates 11 placed on one another, thecontact part and all the busbars of said plates being housed in avertical chlorine-resistant supporting frame 20. The frame has the shapeof a trough with the holes for securing the anode busbars made as metalclamps 21.

The cover has holes 22 to bring out common anode busbar 23. The contactpart of the anodes assembled in vertical units is bolted in metal plateclamps which are secured to common busbar 23.

Anodes 11 assembled in vertical rows are secured to the anode busbarswith the anodes projecting outwardly on both sides of the supportingchlorine-resistant frame 20 (FIG. 4).

In compliance with the invention, the anode set can be made as verticalrows of anodes secured in the vertical chlorine-resistant supportingframes, with the anodes pro jecting outwardly from the frame in onedirection (FIGS. 5 and 6).

Insulation of the anode contact parts and their power supply system iseffected by filling them with concrete and bituminol.

Each anode unit of the elementary electrolytic cell is installed so thatthe anodes enter the clearance between the neighboring box-shapedcathode elements 12 covered with a metal screen.

The cathode of the elementary electrolytic cell is manufactured as acentral metal housing 24 (FIG. 12) with rows of symmetrical cathodepockets 12 covered with a screen and located on both sides of thehousing. The housing serves as a current lead to the pockets and haspipe unions for discharge of alkalies and hydrogen.

In compliance with the invention, the cathodes of the elementaryelectrolytic cells can employ both laminated and deposited diaphragms,for which purpose the edges of the cathode pockets and the upper andlower edges of the cathode housing, mounting said cathode pockets havespecial slots 25 to insert and secure the edges of a laminated diaphragm26 with putty 27 (FIG. 7). It is known that a laminated diaphragm ismore uniform than a deposited one. The use of the laminated diaphragmtherefore permits reduction of requirements to the brine supply of theelectrolyzer. The cathode pockets represent a metal frame with a screenwelded along the upper and lower perimeters, said frame being connectedto the cathode housing. The frame of the cathode pockets consists oflateral metal strips 28, serving as current-carrying busbars, andvertical metal strips 29 (FIG. 13) connecting said busbars along theaxis, said strips 29 also supporting the screen and distributing currentin this screen.

In compliance with the preferred embodiment of the invention, theelementary electrolytic cells are equipped with cathodes havingelectrolysis cells 30 of various sizes formed by cathode pockets 12 andused to house the anodes. Owing to this, during the replacement of thediaphragm, the service life of which is shorter than that of the anodes,the cathodes of the elementary electrolytic cells are replaced by thecathodes with narrower electrolytic cells, providing for the requiredinter-pole distance with due regard to the anode wear. The use of thecathode sets with different width of electrolytic cells results in asignificant saving in electricity.

It is not necessary to manufacture two or more sets of cathodes withdifferent cells for all the electrolyzers. It is quite sufiicient tohave half of the sets of cathodes with electrolytic cells whose sizewill be rated at the thickness of the anodes before replacement of thediaphragm, and half of the sets with the sizes rated at the thickness ofthe anodes after replacement of the diaphragm, that is, the number ofthe cathode sets should correspond to the number of cells inelectrolyzers.

In compliance with the invention, the cathode set is arranged in theelementary electrolytic cell by installing the cathodes on the base ofthe anode set so that the anodes of the anode set symmetrically entercells 30 between cathode pockets 12.

Irrespective of the construction, the cathodes of the elementaryelectrolytic cells are equipped with busbars to deliver current. Thecathode busbar coated with rubber or some other chlorine-resistantmaterial is brought out to the top through holes 31 in the cover, and isconnected to the busbars of the neighboring electrolytic cells.

Through the invention is described in connection with the preferredembodiment, it is evident that changes and modifications may be madetherein without departing from the spirit and scope of the invention, asthose skilled in the art will easily understand. For instance, an anodepower supply provided with the help of metal clamps can be alsoaccomplished with the anodes secured in the cover, the elementaryelectrolytic cells being equipped with two or more covers, theelementary electrolytic cell having, depending on its selected outputtwo or more cathodes made as a central housing with symmetricallylocated parallel rows of cathode pockets; instead of a metal screen, thecathode pockets can be covered with perforated sheet metal.

These changes and modifications are considered to be within the spiritand scope of the invention and the appended claims.

What is claimed is:

1. An electrolyzer for the production of chlorine, hydrogen and alkalisfrom salt solutions, said electrolyzer comprising a non-conductingcasing having a bottom and upstanding walls; at least one anode assemblydisposed within said casing and comprising a current-conducting platemounted vertically on the bottom of said casing and including anodessecured to said plate, said anodes being in the form of rectangularplates secured at right angles to said current-conducting plate onopposite sides thereof, all the anodes of said anode assembly beingparallelconnected to said current-conducting plate; at least oneperforated cathode mounted on the bottom of said casing and comprising aplurality of parallel fiat hollow cathode boxes, one end of each saidbox being connected to a common duct through which electrolysis productsformed at the cathode are to be discharged, so that the inner space ofsaid cathode boxes communicates with the inner space of said duct, saidcathode being comb-shaped and including cathode fingers formed by saidboxes the disposition of which is such that said hollow cathode boxesare interposed between said anodes of said anode assembly; a porousdiaphragm on the perforated cathode surface; and a non-conducting coverwhich closes the electrolyzer.

2. An electrolyzer for the production of chlorine, hydrogen and alkalisfrom salt solutions, said electrolyzer comprising a non-conductingcasing have a bottom and upstanding walls; at least one anode assemblydisposed within said casing and comprising a current-conducting platemounted vertically on the non-conducting bottom of said casing andanodes in the form of rectangular graphite plates, one-half of saidanodes being secured at one end to one vertical surface of saidcurrent-conducting plate and the other half of said anodes being securedto the other vertical surface of said current-conducting plate toprovide a symmetrical disposition of said anodes at both sides of saidcurrent-conducting plate at right angles thereto in rows arranged oneadjacent the other; metal cathodes mounted on said non-conducting bottomof said casing and comprising at least one fiat porous verticallydisposed box constituted of a perforated metal and having one endconnected to a common duct through which electrolysis products formed atthe cathode are to be discharged, so that the inner space of saidcathode boxes communicates with said duct, said cathodes being mountedso as to place said perforated metal boxes in the intervals between rowsof said anodes of said anode assembly, provision being made in thecathodes which are disposed between a wall of said casing and said anodeassembly for one row of said hollow boxes connected to one side of saidcommon duct and arranged between the anode rows of said anode assembly,while in the cathodes disposed between two said anode assembliesprovision is made for two rows of said perforated metal boxes connectedsymmetrically on both sides of said common duct, one row of saidperforated metal boxes being arranged between the anodes of one of saidtwo anode assemblies, and the other row of said perforated metal boxesbetween the anodes of the other anode assembly; a porous diaphragm onthe external perforated surface of said cathodes; and a non-conductingchlorine-resisting cover which closes the electrolyzer.

3. An electrolyzer according to claim 2, wherein the current-conductingplates of said anode assemblies, the busbars to said anode assembliesand the busbars to said cathodes are coated with a chlorine-resistantmaterial.

4. An electrolyzer according to claim 2, wherein the current-conductingplates of said anode assemblies and the busbars of said anode assembliesare made from a chlorine-resistant material, the inoperative surfaces ofsaid cathodes and the surfaces of said cathode busbars cathodes whichcontact moist chlorine and chlorine-containing electrolyte being coatedwith a chlorine-resistant material.

5. An electrolyzer for the production of chlorine, hydrogen and alkalisfrom salt electrolytes, said electrolyzer comprising a non-conductingcasing having a bottom and upstanding walls and including non-conductingpartitions forming a plurality of separate sections; anode assembliesdisposed in said sections and comprising current-conducting platesmounted vertically on the non-conducting bottom of said casing andanodes in the form of rectangular plates secured at one end thereof tothe opposite vertical surfaces of said current-conducting plates atright angles thereto; comb-shaped cathodes including cathode fingersmade from a perforated metal in the form of hollow, flat verticallydisposed boxes connected to common ducts through which electrolysisproducts formed at the cathodes are to be discharged, the inner space ofsaid ducts communicating with the inner space of said cathode boxes,said cathodes being mounted on the non-conducting bottom of the casingso as to place said hollow boxes between said anodes of said anodeassemblies; a diaphragm on the perforated surfaces of said cathodes;non-conducting covers which close said sections from the top; busbars tosaid anode assemblies and busbars to said cathodes arranged so as toinsure parallel connection of all the anodes in each of said sectionsand also to insure parallel connection of all the cathodes in each ofsaid sections, means for current passage consecutively through allsections of the electrolyzer and shunting means for de-energizingseparate sections as desired.

6. An electrolyzer according to claim 5, wherein all said sections areelectrically connected in parallel.

7. An electrolyzer according to claim 5, wherein each section isseries-connected to respective sections of adjacent electrolyzers.

8. An electrolyzer according to claim 5, wherein said partitionsseparating said casing into sections have orifices below the electrolytelevel, whereby each section is in fluid communication with adjacentsections, said orifices being closable.

9. An electrolyzer for the production of chlorine, hydrogen and alkalisfrom salt solutions, said electrolyzer comprising a non-conductingcasing having a bottom and upstanding walls; at least one anode assemblydisposed within said casing and comprising a current-conducting platemounted vertically on the bottom of said casing and graphite anodes inthe form of rectangular plates secured at one end thereof to thevertical opposite surfaces of said plate at right angles thereto, so asto form on both sides of said current-conducting plate at least two rowsof said anodes arranged one above another, means providing parallelconnection of all the anodes of said anode assembly; metal cathodes,each cathode comprising a plurality of hollow flat vertically disposedboxes made from a perforated metal and connected to a common ductthrough which electrolysis products formed at the cathodes are to bedischarged, and having a comb-type structure in which cathode fingersare formed by said hollow vertically disposed boxes, said comb-shapedcathodes being arranged so as to place said vertical boxes in theintervals between the rows of said anodes of said anode assembly withclearance between the surface of said anodes and the surface of saidhollow boxes, a part of said cathodes being adapted for use withpartially worn anodes and having accordingly a greater width of saidhollow boxes in order to maintain the prescribed clearance where theanodes in the anode assemblies are partially worn and are accordinglythinner.

10. An electrolyzer according to claim 1 wherein a plurality of anodeassemblies are provided and the anode plates of the anode assemblies ateach end extend from one side of the respective current conductingplates.

References Cited UNITED STATES PATENTS 2,5 56,830 6/1951 Thrune 2042942,868,712 1/1959 Deprez 204---225 XR 3,342,717 9/1967 Leduc 204--252 XR1,287,156 12/ 19 18 Whitehead 204253 1,357,401 11/1920 Jewell 2042831,407,313 2/ 1922 Allen 204-253 1,545,384 7/ 1925 Ashcroft 2042441,766,875 6/ 1930 Buck 204253 2,222,979 11/ 1940 Lemaire 204-2822,872,406 2/ 1959 Buchanan 204297 2,920,028 1/1960 Forbes 2042533,022,244 2/ 1962 Le Blanc et al 204283 FOREIGN PATENTS 1,346,504 11/1963 France.

I. H. MACK, Primary Examiner D. R. VALENTINE, Assistant Examiner US. Cl.X.R. 204283, 253

